The present invention relates to 2,2,6-trimethyl-1-cyclohexen-1-ylacetaldehyde (or "beta-cyclohomocitral") produced by, interalia, a novel process described and claimed in copending Application for U.S. Pat. No. 507,414 filed on Sept. 19, 1974 and novel compositions using such beta-cyclohomocitral to alter the flavor and/or aroma of consumable materials.
There has been considerable work performed relating to substances which can be used to impart (or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product. Fruity, woody and tea aromas as well as woody-tea and fruity-tobacco tastes are particularly desirable for many uses in foodstuff flavors. Woody, camphoraceous, green and earthy notes are desirable in several types of perfume compositions. Sweet, rich-tobacco, floral, fruity, green, woody, "damascenone-like" and earthy notes are desirable in tobacco flavoring compositions.
Arctander, "Perfume and Flavor Chemicals", 1969 discloses the use in perfume compositions and flavors of "cyclocitral", "dehydro-beta-cyclocitral", "isocyclocitral", "alpha-cyclocitrylidene acetaldehyde" and "beta cyclotrylidene acetaldehyde", thus:
I. "760: CYCLOCITRAL PA1 Ii. "761: iso-CYCLOCITRAL PA1 Iii. "762: alpha CYCLOCITRYLIDENE ACETALDEHYDE ##SPC4## PA1 Mild, floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity to the odor of hydrogenated Ionones. PA1 Suggested for use in perfume compositions. It brings a certain amount of floral lift to Rose compositions, and performs fairly well even in soap. However, the cost of the rarely offered and never readily available lots are rather discouraging to the perfumer, and it is most conceivable that this material can be left out of the perfumer's library without any great loss . . . " PA1 iv. "763: beta-CYCLOCITRYLIDENE ACETALDEHYDE PA1 v. "869: DEHYDRO-beta-CYCLOCITRAL (Safranal) PA1 i. Reacting beta-ionone having the formula: ##SPC8## PA1 in the absence of dimethyl formamide with a peralkanoic acid having the formula: ##EQU2## (wherein R is hydrogen, methyl or ethyl) to form beta-ionone enol ester having the formula: ##SPC9## PA1 and not the expected beta-ionone epoxide having one of the formulae: ##SPC10## PA1 ii. hydrolyzing the beta-ionone enol ester in the presence of base (aqueous or alcoholic) to form beta-cyclohomocitral. PA1 i. The reaction is preferably carried out at temperatures of from 15.degree.C up to about 75.degree.C. Lower temperatures result in slower and less complete reaction and higher temperatures than 75.degree.C result in lower yields of the desired product and significantly higher percentages of by-products. The most preferred temperature of reaction is 25.degree.C. PA1 ii. A slight molar excess (from 10 up to 15 percent) of peracetic acid gives a slightly higher yield of product. A large excess (about 200 percent), however, results in the formation of dihydroactinodiolide having the structure: ##SPC11## PA1 in about 30-35 percent yield when no buffer (e.g., potassium acetate) is present in the reaction mass; PA1 iii. Where potassium carbonate is substituted for potassium acetate as a buffer, the yield of product obtained is substantially the same; PA1 iv. On the other hand, a slightly lower yield of product is obtained by substituting sodium acetate for potassium acetate as the buffer; PA1 v. Substitution of formic acid for acetic acid in the reaction mass gives rise to a lower yield of product. PA1 vi. Any solvent inert to the action of peralkanoic acids may be used in this first oxidation reaction using alkanoic acids. For instance, the use of cyclohexane or chloroform as a solvent does not have an appreciable effect on the yield of product; PA1 vii. Omission of the buffer (i.e., thus performing the reaction under strongly acidic conditions) results in an incomplete reaction, lower yield and greater quantity of by-product(s); PA1 viii. The use of dimethyl formamide as solvent results in the exclusive formation of beta-ionone epoxide having the structure: ##SPC12## PA1 in about 70-75% yield and, accordingly, the presence of dimethyl formamide must be avoided; PA1 ix. The use of monoperphthalic acid (formed in situ from phthalic anhydride and hydrogen peroxide) yields beta-ionone epoxide in 60-70 percent yield. The use of perbenzoic acid in place of peralkanoic acid has also been used to make beta-ionone epoxide R. Yves, et al., Hevl. Chim. Acta, 29, 880 (1946). PA1 p-Hydroxybenzyl acetone; PA1 Geraniol; PA1 Acetaldehyde; PA1 Maltol; PA1 Ethyl methyl phenyl glycidate; PA1 Benzyl acetate; PA1 Dimethyl sulfide; PA1 Vanillin; PA1 Methyl cinnamate; PA1 Ethyl pelargonate; PA1 Methyl anthranilate; PA1 Isoamyl acetate; PA1 Isobutyl acetate; PA1 Alpha ionone; PA1 Ethyl butyrate; PA1 Acetic acid; PA1 Gamma-undecalactone; PA1 Naphthyl ethyl ether; PA1 Diacetyl; PA1 Ethyl acetate; PA1 Anethole; PA1 Isoamyl butyrate; PA1 Cis-3-hexenol-1; PA1 2-Methyl-2-pentenoic acid; PA1 Elemecine (4-allyl-1,2,6-trimethoxy benzene); PA1 Isoelemecine (4-propenyl-1,2,6-trimethoxy benzene); and PA1 2-(4-hydroxy-4-methylpentyl) norbornadiene prepared according to U.S. Application for letters Patent 461,703 filed on Apr. 17, 1974 PA1 I. synthetic Materials: PA1 Ii. natural Oils
Alpha-cyclocitral = (2,2,6-trimethyl-5-cyclohexen-1-carboxaldehyde). beta-cyclocitral = (2,2,6-trimethyl-6-cyclohexen-1-carboxaldehyde). Both isomers are known and have been produced separately. ##SPC1## PA2 Very rarely offered commercially. These particular cyclocitrals have little or no interest to the creative perfumer, but they have served as part of many pieces of proof that isomers (alpha-beta) do often have different odors." PA2 A mixture of two chemicals: PA2 2,6,6-trimethyl-1-cyclohexenyl-beta-acrolein. ##SPC5## PA2 Sweet-woody, rather heavy odor, resembling that of beta-Ionone. More fruity than really floral, but not as tenacious as the Ionone. PA2 Suggested for use in perfume compositions, but since it does not offer any new or unusual odor characteristics, and it cannot be produced in economical competition to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer . . . " PA2 2,6,6-trimethyl-4,4-cyclohexadiene-1-carboxaldehyde ##EQU1## Very powerful, sweet, green-floral and somewhat tobacco-herbaceous odor of good tenacity. In extreme dilution reminiscent of the odor of Safran (Saffron). PA2 Interesting material for fresh topnotes, as a modifier for aldehydic-citrusy notes, as a green-floral topnote in flower fragrances, etc. It blends excellently with the aliphatic Aldehydes, with Oakmoss products and herbaceous oils . . . " PA2 Beta-ethyl-cinnamaldehyde; PA2 Eugenol; PA2 Dipentene; PA2 Damascenone; PA2 Maltol; PA2 Ethyl maltol; PA2 Delta undecalactone; PA2 Delta decalactone; PA2 Benzaldehyde; PA2 Amyl acetate; PA2 Ethyl butyrate; PA2 Ethyl valerate; PA2 Ethyl acetate; PA2 2-Hexenol-1,2-methyl-5-isopropyl-1,3-nonadiene-8-one; PA2 2,6-Dimethyl-2,6-undecadiene-10-one; PA2 2-Methyl-5-isopropyl acetophenone; PA2 2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene; PA2 Dodecahydro-3a-6,6,9 a-tetramethyl naphtho-(2,1-b)-furan PA2 4-Hydroxy hexanoic acid, gamma lactone; PA2 Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No. 3,589,372 issued on June 29, 1971. PA2 Celery seed oil; PA2 Coffee extract; PA2 Bergamot Oil; PA2 Cocoa extract; PA2 Nutmeg oil; PA2 Origanum oil
3,5,6-trimethyl-3-cyclohexen-1-carboxaldehyde (meta)cyclocitral). ##SPC2## PA3 2,4,6-trimethyl-4-cyclohexen-1-carboxaldehyde (symmetric-iso-cyclocitral). ##SPC3## PA3 Powerful, and diffusive, foliage-green, "dark" weedy and dry odor, sometimes described as "Flower-shop odor". The earthy and wet-green notes are quite natural in high dilution and resemble the odor of stems from plants and flowers fresh from the soil. PA3 Finds use in perfume compositions where it blends excellently with Oakmoss products (compensates for sweetness and lifts the topnote), with Ionones (freshness), Geranium and Galbanum (enhances the green and "vegetable" notes), etc . . ."
Safranal and beta-cyclocitral are disclosed as volatile constituents of Greek Tobacco by Kimland et al., Phytochemistry 11 (309) 1972. Beta-cyclocitral is disclosed as a component of Burley Tobacco flavor by Demole and Berthet, Helv, Chim. Acta. 55 Fasc-6, 1866 (1972).